US5432224A - Moldable composition, process for producing sintered body therefrom and products from same - Google Patents

Moldable composition, process for producing sintered body therefrom and products from same Download PDF

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US5432224A
US5432224A US07/733,979 US73397991A US5432224A US 5432224 A US5432224 A US 5432224A US 73397991 A US73397991 A US 73397991A US 5432224 A US5432224 A US 5432224A
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composition
component
binder
powder
weight
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Jiroh Ryuhgoh
Kohshi Kawamoto
Tadahiro Osanaga
Yoshiroh Nakata
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Sanyo Chemical Industries Ltd
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Sanyo Chemical Industries Ltd
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Priority claimed from JP63036380A external-priority patent/JPH01212271A/ja
Priority claimed from JP10850688A external-priority patent/JPH01278558A/ja
Priority claimed from JP63167988A external-priority patent/JPH0219401A/ja
Priority claimed from JP63297011A external-priority patent/JPH0641601B2/ja
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Priority to US07/733,979 priority Critical patent/US5432224A/en
Assigned to SANYO CHEMICAL INDUSTRIES, LTD. reassignment SANYO CHEMICAL INDUSTRIES, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NAKATA, YOSHIROH, KAWAMOTO, KOHSHI, OSANAGA, TADAHIRO, RYUHGOH, JIROH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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    • C04B35/632—Organic additives
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    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C04B35/6346—Polyesters
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    • C04B35/63488—Polyethers, e.g. alkylphenol polyglycolether, polyethylene glycol [PEG], polyethylene oxide [PEO]
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    • C04B35/638—Removal thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • This invention relates to moldable metallic and/or ceramic composition, to process for producing a sintered body therefrom and to products resulting from same.
  • thermoplastic binders such as polypropylene, methacrylate copolymer, polystyrene, ethylene-vinyl acetate copolymer, low density polyethylene, and combinations of them
  • plasticizer or lubricants such as paraffin wax, diethyl phthalate, and stearic acid.
  • a moldable composition which comprises a metallic powder or a mixed powder of metallic and ceramic powder, mixed with an organic binder comprising at least one synthetic resin component (A) having a heat deformation temperature of 130° C. or higher, with or without at least one other component (B) having a melting point of 30° C.-100° C., or combination thereof with other thermoplastic component (C), having a heat deformation temperature of 130° C. or less; or by a moldable composition, which comprises a sinterable particulate material, mixed with an organic binder comprising at least one secondary or tertiary amine (D), or combination thereof with at least one thermoplastic resin (E).
  • FIG. 1 is a perspective view of a specimen.
  • FIG. 2 is a cross sectional view illustrating the method for measuring deformation of a specimen.
  • FIG. 3 is a cross sectional view illustrating the deformed amount (h).
  • Said synthetic resin component (A) has a heat deformation temperature of usually 130° C. or higher, preferably 150° C. or higher, as measured accordinging to ASTM D648 using a load of 4.6 Kg/cm 2 .
  • Suitable synthetic resins include thermoplastic resins, for example, polyacetals, including homopolymers of trioxane, and copolymers of trioxane with ethylene oxide, dioxorane, substituted dioxorane, 1,4-dioxane or the like; polyaryl ethers, such as polyphenylene oxides, polyphenylene sulfides; polyamides, such as nylons 6, 11, 12 and 66, and copolymers of them; polycarbonates; polyesters, such as polyethylene terephthalates and polybutylene terephthalates; polysulfones, such as polyaryl sulfones, polyether sulfones; polyether ketones, polyvinylidene fluorides, and the like, as well as mixtures of two or more of them.
  • thermoplastic resins for example, polyacetals, including homopolymers of trioxane, and copolymers of trioxane with ethylene oxide, dioxoran
  • polyacetals preferred are polyacetals, polyphenylene oxides, polysulfones, polycarbonates, polyesters and polyamides. Particularly preferred are polyacetals, in view of their low melt viscosity and facilities for molding and thermal decomposition.
  • thermoplastic resins As at least a part (preferably 10-40%)of said component (A), there may be used one or more crosslinked thermoplastic resins and/or thermosetting resins.
  • thermoplastic resins include resins of addition polymerization type [for example, those mentioned below as examples of thermoplastic resins (E), such as acrylic resins, olefinic resins, styrene copolymers and other vinyl polymers], copolymerized with one or more crosslinking monomers.
  • E thermoplastic resins
  • Suitable crosslinking monomers include, for example, bis(meth)acrylamides (bisacrylamides and bismethacrylamides; similar expressions are used hereinafter), such as N,N'-methylenebis(meth)acrylamides; polyvinyl compounds, such as divinylbenzene, divinyltoluens, divinylether, divinylketone, trivinylbenzenes and the like; polyesters of unsaturated mono- or poly-carboxylic acids with polyols, such as ethylene glycol di(meth)acrylates, trimethylolpropane Di(meth)acrylates, glycerin tri(meth)-acrylates; and poly(meth)allyl ethers of polyols, such as di(meth)allyl ethers of alkylene glycols (such as ethylene glycol).
  • bis(meth)acrylamides bisacrylamides and bismethacrylamides; similar expressions are used hereinafter
  • polyvinyl compounds such
  • bis(meth)acrylamides preferred are bis(meth)acrylamides, polyvinyl compounds, and polyesters of unsaturated mono- or polycarboxylic acids with polyols.
  • Particularly preferred re N,N'-methylene bis-(meth)acrylamides, divinylbenzenes, thylene glycol di(meth)acrylates, and trimethylolpropane Di(meth)acrylates.
  • Illustrative examples-of such resins are crossliked polystyrenes, and crosslinked styrene(meth)acrylate copolymers.
  • crosslinked thermoplastic resins include polycondensation type resins [for example, polyesters (such as polyethylene terephthalates), polyamides (such as Nylon 66), polyimides, polysulfones, poly-paraphenylenes], crosslinked with one or more crosslinkers.
  • polycondensation type resins for example, polyesters (such as polyethylene terephthalates), polyamides (such as Nylon 66), polyimides, polysulfones, poly-paraphenylenes
  • crosslinked with one or more crosslinkers for example, polyesters (such as polyethylene terephthalates), polyamides (such as Nylon 66), polyimides, polysulfones, poly-paraphenylenes
  • crosslinkers include compounds having three or more reactive groups causing polycondensation, for instance, polycarboxylic acids, such for instance, polycarboxylic acids, such as aromatic and aliphatic polycarboxylic acids (benzene tricarboxylic acids and the like); polyamines, such as aromatic and aliphatic polyamines (polyalkylene polyamines, such as diethylene triamine and the like); polyols, such as polyhydric alcohols (glycerin, trimethylol propane and the like) and alkylene oxide (such as ethylene oxide and/or propylene oxide) adducts of these compounds containing 3 or more active hydrogen atoms.
  • polycarboxylic acids such for instance, polycarboxylic acids, such as aromatic and aliphatic polycarboxylic acids (benzene tricarboxylic acids and the like)
  • polyamines such as aromatic and aliphatic polyamines (polyalkylene polyamines, such as diethylene triamine and the like); poly
  • thermosetting resins include, for example, phenolic resins, urea resins, cured epoxy resins, and polyurethane resins.
  • Semi-synthetic resins such as nitrocellulose and cellulose acetates may also be used.
  • resins are usually used in the form of powder.
  • resin powder may be those produced in powder form, or those powdered after production of resins.
  • Particle size of these resins is not particularly restricted, and can vary according to particle size of particulate material (metallic and/or ceramic powder).
  • these resins Preferably, these resins have an average diameter smaller than that of the particulate material, particularly smaller than a half of the latter.
  • Said component A is used preferably in combination with at least one other component (B) having a melting point of 30° C.-100° C., preferably 50°-100° C.
  • Suitable examples of said component B are polyethers, such as those represented by the formula: ##STR1## wherein R is a residue of active hydrogen atom-containing compound; R' is H, a mono-valent hydrocarbon radical or acyl radical; A is an alkylene radical containing 1-4 carbon atoms, or an alkylene radical containing 2-4 carbon atoms, having an aryl-substituent; m is an integer of 1-8 (preferably 1-3); and n is an integer of at least 2 (preferably at least 4).
  • Examples of active hydrogen atom-containing compounds, constituting the residue R are water; alcohols, for instance, low molecular weight polyols (such as ethylene glycol, propylene glycols, 1,3- and 1,4-butane diols, 1,6-hexane diol, neopentyl glycol, cyclohexylene glycol, glycerin, trimethylol propane, pentaerythritol, sorbitol, sucrose and the like), and monohydric alcohols (such as aliphatic alcohols containing 1-20 carbon atoms and aromatic alcohols); phenols, for example, polyhydric phenols (bisphenols, such as bisphenol A), and mono-hydric phenols [phenol, naphthols, alkyl(C 1 -C 12 )- or aryl-substituted phenols, such as octylphenol, nonylphenol, dodecylphenol and phenylphenols];
  • Suitable mono-valent hydrocarbon radicals in R' include, for example, alkyl radicals containing 1-20 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, octyl and decyl radicals; aromatic hydrocarbon radicals, including aryl radicals (such as phenyl and naphthyl), aralkyl radicals (such as benzyl and phenethyl), and alkylaryl (octylphenyl and nonylphenyl).
  • suitable acyl radicals in R' are those of carboxylic acids containing 2-20 carbon atoms, such as acetyl.
  • R' preferred are H and C 1 -C 4 alkyl, particularly H, methyl and ethyl.
  • alkylene radicals A examples include alkylene radicals, such as methylene, ethylene, propylene, butylene, and phenyl-ethylene groups. Among these, preferred are ethylene, propylene, butylene and combinations of ethylene with propylene. Particularly preferred is ethylene.
  • Molecular weight of polyethers can vary widely, but preferably up to about 20,000.
  • suitable polyethers are polyalkylene glycols, including those having a molecular weight of usually about 150- about 20,000, preferably 1000-10,000, and containing 2-4 carbon atoms in each alkylene group, such as polyethylene glycols (MW 150-20,000), polypropylene glycols (MW 200-5,000), polytetramethylene glycols (MW 200-3,000), copolymers of ethylene oxide and propylene oxide (MW 200-20,000).
  • waxes such as petroleum wax, natural waxes (such as bees wax), and synthetic waxes (such as polyethylene wax); low molecular weight solid materials, such as fatty acids (C 10 -C 20 or more, such as stearic acid), salts thereof (soaps and metal soaps such as aluminum stearate), fatty alcohols (C 12 -C 20 or more, such as stearic alcohol), fatty amines (C 12 -C 20 or more, such as mono- and di-stearyl amines), and various surfactants (such as those written in U.S. Pat. No. 4,331,447); and mixtures of two or more of them.
  • fatty acids C 10 -C 20 or more, such as stearic acid
  • salts thereof salts thereof (soaps and metal soaps such as aluminum stearate)
  • fatty alcohols C 12 -C 20 or more, such as stearic alcohol
  • fatty amines C 12 -C 20 or more
  • polyethers particularly polyalkylene glycols, especially polyethylene glycols, in view of compatibility, when used in conjunction with a polyacetal as the component A.
  • the binder may contain, other thermoplastic component (C), having a heat deformation temperature of 130° C. or less and a melting point of more than 100° C., to improve moldability.
  • Suitable components C include, for example, polyethers [those represented by the formula (1) but having higher molecular weight, such as polyethylene oxides]; and polymers of ethylenically unsaturated monomers, including polyolefins (such as polyethylenes, polypropylenes, poly-4-methylpentene-1, polystyrenes, polyalpha-methyl-styrenes, ethylene-vinyl acetate copolymers), and (meth)acrylic polymers [such as poly(meth)acrlates], and two or more of them.
  • polyethers such as polyethylenes, polypropylenes, poly-4-methylpentene-1, polystyrenes, polyalpha-methyl-styrenes, ethylene-vinyl acetate copolymers
  • polymers may vary widely; but preferred are those having a molecular weight of about 1000-about 10 millions, more preferably about 5000-about 5 millions. These polymers have thermal decomposition temperature of usually 150°-600° C., preferably 200°-400° C.
  • polyethylene oxides particularly those having a molecular weight of about 50,000-about 5 millions, with respect to compatibility.
  • the moldable composition comprises a metallic powder, a ceramic powder or a mixed powder of metallic and ceramic powder, mixed with an organic binder comprising at least one amine (D), selected from the group consisting of secondary amines and tertiary amines.
  • Suitable examples of said amine (D) are monoamines and polyamines (including ones containing a primary amino group in addition to the secondary and/or tertiary amino group), having an amine value of usually 50-500, preferably 40-400 and a molecular weight of usually at most 3000, preferably 100-1000.
  • Preferable amines include those represented by the formula: ##STR2##
  • R 1 is a monovalent hydrocarbon radical containing 5-30 carbon atoms
  • R 2 is hydrogen atom or a monovalent hydrocarbon radical containing 1-30 carbon atoms
  • R 3 is hydrogen atom or a monovalent hydrocarbon radical containing 1-30 carbon atoms
  • R 4 is hydrogen atom or a monovalent hydrocarbon radical containing 1-5 carbon atoms
  • A is an alkylene group containing 2-4 carbon atoms, which may have an aryl side group
  • n is an integer of 0-5.
  • hydrocarbon radical R 1 examples include aliphatic hydrocarbon radicals, for example, alkyl groups (such as pentyl, 2-ethylhexyl, octyl, dodecyl, hexadecyl, octadecyl, eicosyl and docosyl groups), alkenyl groups (such as myristoleyl, palmitoleyl, oleyl and rinoleyl groups); cycloaliphatic hydrocarbon radicals, for instance, cycloalkyl groups (such as cyclohexyl group); and aromatic hydrocarbon radicals, for example, aryl groups (phenyl and naphthyl groups), aralkyl groups (such as phenethyl, phenyloctyl and phenyldodecyl groups), alkylaryl groups (such as methylphenyl, octylphenyl and dodecylphenyl).
  • alkyl groups such as pent
  • aliphatic hydrocarbon radicals particularly those containing 10-30 carbon atoms.
  • Suitable hydrocarbon radicals in R 2 and R 3 include the above-mentioned monovalent hydrocarbon radicals containing 5-30 carbon atoms, and lower aliphatic hydrocarbon radicals, for example, lower alkyl groups (such as methyl, ethyl, n- and i-propyl and butyl groups) and lower alkenyl groups (such as allyl and butenyl groups).
  • Preferred as R 2 are aliphatic hydrocarbon radicals (particularly those containing 1-20 carbon atoms); and preferred as R 3 are aliphatic hydrocarbon radicals (particularly those containing 1-20 carbon atoms) and hydrogen atom.
  • Suitable monovalent hydrocarbon radicals in R 4 are those as mentioned above, containing 1-5 carbon atoms.
  • Plural R 4 s(in case where n is 2 or more) may be the same or different.
  • Preferred as R 4 are methyl and ethyl groups (particularly ethyl group) and hydrogen atom.
  • Suitable examples of said alkylene groups A are inclusive of alkylene proups containing 2-4 carbon atoms, such as ethylene, propylene and butylene groups; and aryl-substituted alkylene groups, such as phenylethylene group.
  • Plural A (in case where n is 2 or more) may be the same or different.
  • preferred are ethylene, propylene and butylene groups, and combination of ethylene and propylene groups, particularly ethylene group.
  • Said n is an integer of 0-5, preferably 0-1.
  • Secondary amines aliphatic amines, for instance, alkyl amines (such as methyl octyl amine, dodecyl octadecyl amine, dioctadecyl amine, di-hardened tallow alkyl amine and didocosyl amine), and alkenylamines (such as octadecyl allyl amine, methyl oleyl amine and dioleyl amine); cycloaliphatic amines, such as octadecyl cyclohexyl amine; and aromatic amines, such as dibenzyl amine, diphenyl amine, phenyldodecyl methyl amine, diphenyldodecyl amine, and N-octadecyl aniline;
  • alkyl amines such as methyl octyl amine, dodecyl octadecy
  • Tertiary amines aliphatic amines, for instance, alkyl amines (such as dimethyl octyl amine, dimethyl decyl amine, dimethyl dodecyl amine, dimethyl coconut amine, dimethyl myristyl amine, dimethyl palmityl amine, dimethyl octadodecyl amine, methyl didodecyl amine, methyl dioctadodecyl amine, trioctyl amine and tridodecyl amine), and alkenylamines (such as dioctadecyl allyl amine, octadecyl diallyl amine, dimethyl oleyl amine, methyl dioleyl amine and dimethyl rinoleyl amine); cycloaliphatic amines, such as methyl octadecyl cyclohexyl amine; and aromatic amines,
  • apiphatic polyamines for example, alkyl-substituted alkylene(C 2 -C 4 ) diamines or dialkylene (C 2 -C 4 ) triamines, such as octadecyl ethylene diamines, tridodecyl propylene diamines and octadecyl tetramethyl diethylene triamines; as well as mixtures of two or more of these amines.
  • cycloaliphatic polyamines such as dodecyl cyclohexylene diamine and methyl octadecyl isophorone diamine
  • aromatic polyamines such as tetradodecyl phenylene diamine, dioctadecyl tolylene diamines, octadecyl xylylene diamines and dioctadecyl diphenylmethane diamine
  • heterocyclic amines such as N-amino dodecylpiperazine and N-octadecyl morpholine
  • alkanol amines such as dodecyl ethanol amine; and mixtures of two or more of them.
  • Said amine (D) may be used together with one or more of organic binders.
  • organic binder there can be used one or more thermoplastic resins (E), such as those obtainable by addition polymerization (polymerization of unsaturated compounds), by polycondensation and by ring-opening polymerization.
  • resins of addition polymerization type include acrylic resins [polymers and copolymers of esters of (meth)acrylic acids, such as polymethyl (meth)acrylates, polyethyl (meth)acrylates, polybutyl (meth)acrylates, polycyclohexyl (meth)acrylates, butyl (meth)acrylate-methyl (meth) acrylate copolymers, butyl (meth)acrylate-dodecyl (meth) acrylate copolymers, butyl (meth)acrylate-acrylonitrile copolymers, methyl (meth)acrylate-acrylamide copolymers, ethyl (meth)acrylate-2-chloroethyl vinyl ether copolymers, methyl (meth)-acrylate-(meth)acrylic acid copolymers, methyl (meth)-acrylate-hydroxyethyl (meth)acrylate copolymers, and butyl (meth)
  • Suitable polycondensation type resins include, for example, polyesters, such as polyethylene terephthalates, polytetramethylene terephthalates and polyethylene sebacates; polyamides, such as Nylon 66; polyimides; polysulfones; poly-pare-phenylenes; and the like.
  • suitable ring-opening polymerization type resins are inclusive of polyethers, such as polyethylene oxides, polypropylene oxides and polytetramethylene glycols.
  • Semi-synthetic polymers such as nitrocellulose, cellulose acetate and ethyl cellulose, may also be used. Two or more of these thermoplastic resins can be used in combination.
  • polyisobutylenes preferred are polyisobutylenes, polymethacrylate esters, polystyrenes, polyethylene oxides, polypropylene oxides and poly-alphamethylstyrenes. More preferred are polymethacrylate esters, polystyrenes and polyethylene oxides.
  • the binder may contain optionally one or more additional components, such as plasticizers, lubricants, surfactants, various coupling agents (such as silane coupling agents), and so on.
  • additional components such as plasticizers, lubricants, surfactants, various coupling agents (such as silane coupling agents), and so on.
  • plasticizers include ester plasticizers, including carboxylates, for example, esters of aromatic mono- or poly- carboxylic acids, such as phthalates (dimethyl, diethyl, dibutyl, diheptyl, di-n-octyl, di-2-ethylhexyl, ditsononyl, diisodecyl, dilauryl, dicyclohexyl and butylbenzyl phthalates, and the like), trimellitates (tris-C 4 -C 11 alkyl trimellitates, such as tris-2-ethylhexyl trimellitate, and the like), benzoates (polyoxyalkylene benzoates, such as polyoxyethylene benzoates, and the like); esters of aliphatic monobasic acids, such as butyl oleate and Glycerin monooleate; esters of aliphatic dibasic acids, such as adipates (dibutyl,
  • lubricants are aliphatic hydrocarbons, liquid paraffins, microcrystalline waxes, natural paraffins, synthetic paraffins, polyolefin waxes, and derivatives of them (such as partially oxidized ones, chlorinated ones and fluorinated ones); higher fatty alcohols, such as lauric, stearyl and oleyl alcohols, and mixed fatty alcohols; higher fatty acids, such as lauric, stearic and oleic acids, and mixed fatty acids (those obtainable from tallow, fish oil, coconut oil, soybean oil, colza oil, rice bran oil and the like), fatty amides (oleylamide, stearylamide, methylene-bis-stearamide, ethylene-bis-stearamide and the like), soaps and metallic soaps (stearates of barium, calcium, zinc, aluminum, magnesium and the like), fatty esters [higher fatty acid esters of monohydric alcohols (such as butyl ole
  • Suitable surfactants include those written in U.S. Pat. No. 4,331,447, for example, anionic surfactants, such as dodecylbenzene sulfonates and polyoxyethylene(4) nonylphenylether sulfates; nonionic surfactants, such as polyoxyethylene(4) stearyl amine, mono- and/or di-ethanol amide of stearic acids; cationic surfactants, such as lauryltrimethylammonium chloride; ampholytic surfactants, such as stearyldimethylcarboxymethyl-betaine; and mixtures of two or more of them.
  • anionic surfactants such as dodecylbenzene sulfonates and polyoxyethylene(4) nonylphenylether sulfates
  • nonionic surfactants such as polyoxyethylene(4) stearyl amine, mono- and/or di-ethanol amide of stearic acids
  • cationic surfactants such as lauryltrimethylammonium chloride
  • Metallic powders employed with the binder in the preparation of the moldable compositions of this invention may be prepared from any metal which is stable in the atmosphere and is reducible to powdered form.
  • materials of metal character that are applicable for use are metals, for example, iron (such as carbonyl iron, atomized iron and reduced iron), nickel (such as carbonyl nickel), cobalt, aluminum, copper, titanium, molybdenum, zirconum, chromium, lead, manganese, wolfram, zinc, tin, beryllium, germanium, magnesium, silicon and boron; and alloys containing two or more thereof, for example, stainless steel, iron-nickel alloy, high speed steel, super alloy, magnetic materials, brass, bronze, monel metal, iron-silicon alloy, iron-boron alloy and the like.
  • iron, and iron alloys such as stainless steel, iron-nickel alloy and high speed steel.
  • Ceramic powders which may be utilized in the invention in conjunction with (or in stead of) metallic powders, include for example, oxides, such as alumina, silica, zirconia, beryllia, magnesia and titania; silicates such as mullite and cordulite; titanates, such as barium titanate; carbides (particularly water non-reactive carbides), such as carbides of silicon, boron, aluminium, wolfram, titanium, zirconium, hafnium, chromium and vanadium, and carbon; nitrides, such as those of silicon, aluminum, boron and titanium; silicides, such as molybdenum disilicide; sulfides, such as cadmium sulfide and zinc sulfide; and so on, as well as mixtures of two or more of them.
  • oxides such as alumina, silica, zirconia, beryllia, magnesia and titania
  • silicates such
  • mixtures of metallic and ceramic powders for example, wolfram carbide-cobalt, and alumina-aluminium.
  • Such mixtures include blends of metallic powder and ceramic powder, and alloys of metallic powder and ceramic powder.
  • particulate materials may contain usual small percentage of impurities or/and additives.
  • sintering aids, molding agents and other additives for improving physical properties may be added by blending merely or by surface-coating onto the materials.
  • the average particle size of these particulate materials can vary widely, for instance, ranging from 0.01 to 50 microns, preferably 0.1 to 20 microns (micron m).
  • the average particle size may vary somewhat larger range, such as from 0.01 to 100 microns, in some case, particularly in case where said amine (D) is used.
  • These particulate materials may be used alone or as a mixture of two or more of such materials of different kinds or different particle sizes. Particulates of less than 0.01 micron diameter are bulky and difficult to handle and result in poor moldability. Particulates of larger than 50 microns are of poor sinterability.
  • the component A having a heat deformation temperature (hereinafter referred to as HDT) of 130° C. or higher, serves for reducing deformation during debinding, as well as imparting flowability to the composition; while components having a heat deformation temperature of less than 130° C. are insufficient for reducing deformation during debinding.
  • the component A may be used in such an amount of generally 20-100%, preferably 30-60%, based on the weight of the binder. Using less than 20% results in molded bodies of poor strength and difficulty in handling.
  • the component B having a melting point of usually 30° C.-100° C., serves for heightening the deformation reducing effects and for accelerating debinding, along with improving flowability to facilitate injection molding.
  • the component B can be used in such an amount of generally 0-80%, preferably 40-70%, based on the weight of the binder. Using more than 80% results in molded products of insufficient strength.
  • the component C may be used in such an amount of generally 0-60%, preferably 0-40%, more preferably 0.1-30%, based on the weight of the binder. Molded bodies obtained by using more than 60% of the component C are likely to be deformed.
  • the particulate material may be used in such an amount of generally 40-70%, preferably 50-80%, based on the volume of the composition.
  • the amount of the particulates is more than 70%, it become difficult to kneading homogeneously them with the binder and to injection mold.
  • Using the particulates in smaller than 40% causes larger deformation of molded bodies during debinding.
  • the amounts of (D) and the particulate material can vary widely, and molding can be attained with use of lower amount of the organic components.
  • (D) and the particulate material may be used in such amounts of generally 0.1-50% preferably 0.1-30%, and usually 50-99.5% preferably 70-99.9%, respectively, based on the weight of the composition.
  • Use of less than 0.1% of (D) or more than 99.9% of the particulate material results in poor moldability; and use of more than 50% of (D) or less than 50% of the particulate material causes reduction of strength of debinded bodies.
  • the amount of the organic binder (E) may be usually 0-49.9% preferably 0.5-29.9%. Use of more than 50% of the binder results in debinded bodies of poor strength.
  • Additional components may be used in such an amount as usually used (for instance 0-40%, preferably 0-30%, based on the weight of the composition.
  • composition of the invention can be produced by mixing or/and kneading the components.
  • Mixing can be carried out by using conventional mixing means, such as a twin-cylinder mixer, a Henschel mixer, a ball mill or the like, followed by drying if necessary.
  • mixing temperature is usually 0°-100° C. preferably 0°-50° C.
  • mixing time is generally 10 minutes-6 hours preferably 30 minutes-2 hours.
  • Mixing with a ball mill or the like may be carried out under dry or wet conditions, at a temperature of usually 0°-50° C., for generally 6-72 hours preferably 6-36 hours. Drying may be done within an air or an atmosphere of an inert gas, at normal pressure or under a reduced pressure, under heating and/or with hot-air. It is preferred drying under non-oxidizing atmosphere (an atmosphere of inert gas, such as nitrogen, argon or the like), or under reduced pressure.
  • Kneading may be carried out under melting by using any of known kneading machines, such as Banbury mixers, Lab Plast Mill®'s (Lab Plast Mill is a registered tradename of TOYO SEIKI SEISAKUSHO, Ltd.), kneaders, pressure kneaders, roll mills, extruders (screw extruders) and the like. Among these, preferred are pressure kneaders and extruders. Kneading temperature is generally 50°-300° C. or higher (such as up to 350° C.), preferably 100°-250° C., more preferably 150°-200° C., and the temperature may be controlled at a constant, increasing or decreasing temperature.
  • Kneading may be carried out at a temperature lower than the heat deformation temperature of a resin powder which is apart of component A. Kneading may be carried out within an air or an atmosphere of an inert gas, preferably under non-oxidizing atmosphere (an atmosphere of inert gas, such as nitrogen, argon or the like) or under reduced pressure (in vacuo). Kneading time is usually 10 minutes-3 hours or longer (such as up to 10 hours), preferably 20 minutes-2 hours, more preferably 30 minutes-an hour.
  • the components may be mixed or kneaded in any order as far as a homogeneous mixture is obtained.
  • Each component or a mixture may be dried before kneading, if neccesary.
  • Suitable kneading methods include, for example, those by charging and kneading all the components at once; those by kneading a part of the components at first, followed by adding thereto the rest and kneading [for instance, those by kneading the organic components at first and then adding thereto the particulate material(s); those by kneading the particulate material(s) with a part of the organic components ⁇ such as said amine (D) or the binder ⁇ at first and then adding thereto the rest of the organic components ⁇ such as the binder or said amine (D) ⁇ and those by adding the organic or binder components afterwards.]
  • the kneaded compositions may be crushed (or granulated) after cooling
  • the moldable compositions thus obtained can be formed into various molded bodies (such as sheet, articles of complicated shape, and so on), by known molding techniques, for example, injection molding, extrusion molding, press molding (such as cold press, compression molding and transfer molding), and the like. Among these, preferred are injection molding. Injection molding may be carried out by means of usual injection molding machines, such as plunger injection machines and screw injection machines.
  • Molding conditions may vary according to the shape of molds and moldable compositions.
  • molding pressure is usually 10-20,000 Kg/cm 2 , preferably 20-10,000 Kg/cm 2 , more preferably 100-3000 Kg/cm 2 , most preferably 200-2000 Kg/cm 2
  • molding temperature is generally 20°-300° C. or higher (such as up to 350° C.), preferably 50°-250° C., more preferably 150°-200° C.
  • Molding may be carried out under reduced pressure (in vacuo) or under non-oxidizing atmosphere (an atmosphere of inert gas, such as nitrogen, argon or the like).
  • the molded articles after demolding are debinded or baked.
  • Debinding or baking process is preferably carried out in an atmosphere of oxidizing gas (such as air), reducing gas (such as hydrogen or carbon mono-oxide) or inert gas (such as nitrogen or argon), under reduced pressure, under normal pressure or under pressure, heating at a rate of usually 1°-500° C./hr, preferably 1°-200° C./hr, more preferably 1°-60° C./hr, most preferably 10°-40° C./hr to a final temperature of usually 150°-500° C. or higher, preferably 160°-400° C., more preferably 160°-350° C., followed by maintaining the above temperature generally for 0-10 hours, preferably for 1-5 hours. It is preferred to debind under an atmosphere of oxidizing gas, such as air.
  • Molded bodies comprising the composition of this invention have no or little tendency of deformation and may be debinded as such, without necessity of burying in particulated material or supporting with a setter.
  • Debinding can be accomplished merely by placing the bodies on a shelf board within a debinding furnace.
  • an atmosphere-flowable shelf board By using an atmosphere-flowable shelf board, the body surface including the underside can be exposed to the atmospheric gas, whereby debinding time can be shortened.
  • shelf boards include wire sheets, such as stainless steel wire cloth, and support grid or ceramic formed in the shape of lattice.
  • the product from the debinding or baking step is then sintered to obtain the final product.
  • Sintering can be carried out in an atmosphere of oxidizing gas, reducing gas or inert gas, under reduced pressure, under normal pressure or under pressure, heating to a final temperature of usually 600°-2500° C., preferably 600°-2200° C., more preferably 800°-2000° C. Heating rate is usually 50°-1000° C./hr, preferably 50°-300° C./hr.
  • the final temperature is maintained generally for 10 minutes-10 hours, preferably for 30 minutes-3 hours.
  • the degree of vacuum is generally 10 -2 Torr or less, preferably 10 -3 Torr or less.
  • Moldable compositions of the present invention containing as the binder the resin component (A) having HDT of at least 130° C., particularly those containing (A) in conjunction with the component (B) having a melting point of 30° C.-100° C., can provide debinded articles of excellent appearence free from deformation, even at a longer distance (L) between supporting rods (that is even a larger molded articles), or even when is used such a particulate material as stainless steel which is liable to cause deformation during debinding; while moldable compositions comprising low HDT components such as PP and wax, without said component (A), were apt to be deformed by gravity, particularly in case of stainless powder.
  • component (A) in this invention such a resin as polyacetal which has HDT of at least 150° C. and is easily decomposed and using as the component (B) such a low melting component as polyethyleneglycol which is also easily decomposed, debinding can be attained within a short period of time, at lower temperature, in addition to improvement of deformation inhibiting effects.
  • Moldable compositions comprising a particulate material and said amine (D), as another aspect of the present invention, can provide the following effects:
  • Sintered bodies substantially free from residue of impurities, such as carbon, can be obtained.
  • Sintered bodies of high denseness, substantially free from residue of impurities, such as carbon, can be obtained.
  • thermal decomposition of the binder during kneading or molding can be inhibited, and there can be attained sintered articles of stable or constant qualities even when the compounds are used recycling.
  • parts, ratio and % mean parts by weight, weight ratio and % by weight, respectively, unless otherwise specified.
  • PC polycarbonate
  • CO-POM polyacetal copolymer
  • POM polyacetal homopolymer
  • PSF polysulfone
  • PMMA polymethylmethacrylate
  • PP polypropyrene
  • PBA polybutyl acrylate
  • PBM polybutyl methacrylate
  • PEG-4000 polyethylene glycol (MW 4000);
  • PEO polyethylene oxide
  • X-PS Crosslinked polystyrene
  • X-SA Crosslinked sutyrene/acrylate copolymer
  • PW paraffin wax
  • DBP dibutyl phthalate
  • DOA di-octadecyl amine
  • DOA di-octadecyl amine
  • DMOA dimethyl octadecyl amine
  • ODA octadecyl amine
  • E/VAc ethylene-vinyl acetate copolymer
  • FEN-8 powder a mixed powder comprising 92% of iron powder (average diameter of 4 microns) and 8% of nickel powder (average diameter of 10 microns);
  • SUS 304 powder stainless steel 304 powder (average diameter of 10 microns)
  • HDT heat distortion temperature
  • RD relative density
  • BSG bulk specific gravity
  • MC micro-cracking
  • Moldable compositions were prepared by combinations of 56 volume % of iron powder (average diameter of 4 microns) or SUS 304 powder with each of 4 resins (PC, CO-POM, POM and PSF), having HDT of at least 130° C., as written in Table 1.
  • Each composition was kneaded with a pressure kneader, for about 45 minutes at a temperature between 180° C. and 380° C. depending on the resin used, followed by heat pressing at 200°-380° C. to form specimens (100 mm ⁇ 10 mm ⁇ 4 mm) as shown in FIG. 1.
  • Each specimen was put on two supporting rods placed at a certain distance L (10 mm, 20 mm or 30 mm), as shown in FIG.
  • Example 1 was repeated except using each of 2 resins (PMMA and PP), having HDT of less than 130° C., as written in Table 1.
  • Example 1 showed some deformation at longer L, but the specimens of Examples 2, 3 and 4 using resins of at least 150° C. of HDT showed no deformation. 0n the other hand, the specimens of Comparative Examples 1 and 2 resulted in considerable deformation.
  • Moldable compositions were prepared by using as the metallic powder either FEN-8 powder or SUS 304 powder and using as the binder the same POM or CO-POM as in Examples 2 and 3 in admixture with PEG-4000 [melting point: 56° C.], in accordance with the formulation shown in Table 2.
  • Each composition was kneaded with a pressure kneader, for about 45 minutes at a temperature between 150° C. and 180° C., followed by crushing under cooling to obtain an injection moldable compound.
  • each compound was molded into the same specimen as in FIG. 1, using a injection molding machine under conditions of the heating cylinder temperature of 150°-170° C., the mold temperature of 50° C. and the injection pressure of 1500 Kg/cm 2 .
  • Example 3 Each specimen was set in the same manner as in Example 1 and debinded by heating within a circulating furnace at a rate of 20° C./hr to a temperature of 350 C. and maintaining the temperature for 2 hrs to attain a debinding ratio of about 98%, and degree of deformation of the debinded body was evaluated as in Example 1.
  • the debinded specimens showed no deformation, and nothing wrong was observed, such as cracking or blistering.
  • Injection moldable compositions were prepared by repeating Example 5(1) except using the same PP as in Comparative Example 2 in admixture with PW [melting point: 58° C.], in accordance with the formulation shown in Table 2.
  • Example 5(2) was repeated under injection molding conditions of the heating cylinder temperature of 150° C., the mold temperature of 50° C. and the injection pressure of 1500 Kg/cm 2 , and resulted in a debinding ratio of about 85% and degree of deformation as written in Table 2.
  • Example 7 was repeated except that the molded specimen was debinded by heating within a circulating furnace set on stainless steel wire cloth so as to exposing the surface including the underside to circulating hot air to shorten the debinding time. There was obtained a debinded body of good appearence with a debinding ratio of about 98%.
  • Example 7 The debinded body obtained in Example 7 was sintered in a vacuum of 10 -3 Torr or less, at 1250 C. for 2 hrs to obtain a sintered body having RD of 95%.
  • Example 7 Example 7 was repeated except that a stainless steel powder having average diameter of 4.7 micron was used as the metallic powder.
  • the resulting debinded body was sintered in the same manner as in the above (1) to obtain a sintered body having RD of 98%.
  • Examples 1-4 were repeated except using, instead of metallic powder, mixtures of metallic powder and ceramic powder as follows. There were obtained debinded bodies free from deformation.
  • Moldable compositions were prepared by combinations of alumina powder (average diameter of at most 1 micron) or SUS 304 powder, with PBM, PEO (MW: about 20,000), DBP, and DOA or DMOA, according to the formulations (parts) as written in Table 3.
  • Moldable compositions were prepared by repeating Examples 14-17, except using PW or ODA.
  • composition of Examples 14-17 and Comparative Examples 5-12 was injection molded into the same specimen as in FIG. 1, under conditions of the injection pressure of 1500 Kg/cm 2 and the molding temperature of 150° C., followed by debinding for 10 hours (a) or 32 hours (b), and then sintering under conditions:
  • Moldable compositions were prepared, according to the formulations (parts) as written in Table 5, by repeating the procedure of Examples 14-17 except that kneading was carried out at 8° C.
  • Each composition of Examples 18-20 and Comparative Examples 13 and 14 was molded using a screw injection molding machine under conditions of the injection pressure of 1500 Kg/cm 2 and the molding temperature of 150° C. to form a injection molded article, followed by debinding under conditions of the maximum temperature of 400° C. and debinding period of 32 hours, and then sintering under conditions of at 1600° C. for 2 hours within air in case of alumina, or at 1250° C. for 2 hours under reduced pressure in case of stainless.
  • Moldable compositions were prepared, according to the formulations as written in Table 7. Using a Lab Plast Mill®, PBM and PEO were charged and melted at 130° C. and at 30 rpm rotor revolution. Then, alumina powder or stainless powder and montan wax were added gradually, followed by kneading at 130° C. and at 50 rpm for 30 minute and then crushing.
  • Each composition of Examples 21-24 and Comparative Examples 15 and 16 was molded using a screw injection molding machine under conditions of the injection pressure of 1500 Kg/cm 2 and the molding temperature of 150° C. to form a injection molded article, followed by debinding under conditions of the following (i) or (ii), and then sintering under conditions of at 1600° C. for 2 hours within air in case of alumina, or at 1250° C. for 2 hours under reduced pressure in case of stainless.
  • the resulting debinded body was sintered in the same manner as in Example 9 (1) to obtain a sintered product having RD of 95%.
  • Example 7(1) was repeated except that kneading was carried out under an atmosphere of nitrogen to obtained a kneaded mixture.
  • the kneaded mixture was molded under the same conditions as Example 7(2) , except that molding was carried out under an atmosphere of nitrogen, and the mixture was molded recycling 10 times under the same conditions as above. Even after 10 times recycling, there were no substantial reduction of the amount of the binder by thermal decomposition and no change in moldability.
  • the resulting molded product was debinded under the same conditions as in Example 24 to obtain a debinded body having good appearance and a debinding ratio of about 92%.
  • the resulting debinded body was sintered in the same manner as in the above (1) to obtain a sintered product having RD of 95%. Dimensional accuracy of each part of the sintered product was within tolerance limits of 0.2%.
  • the amount of the binder was reduced about 2% by thermal decomposition after 10 times recycling, and the resulting sintered product after 10 times recycling showed maximum 0.5% of dimensional inaccuracy as compared with the first (non-recycled) product.

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US07/733,979 1988-02-18 1991-07-22 Moldable composition, process for producing sintered body therefrom and products from same Expired - Fee Related US5432224A (en)

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JP63036380A JPH01212271A (ja) 1988-02-18 1988-02-18 成形用組成物および使用法
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JP63-108506 1988-04-30
JP63167988A JPH0219401A (ja) 1988-07-06 1988-07-06 成形用組成物、製造法および使用法
JP63-167988 1988-07-06
JP63297011A JPH0641601B2 (ja) 1988-11-24 1988-11-24 成形用組成物
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US20010050155A1 (en) * 2000-06-07 2001-12-13 Billiet Romain L. Method for rapid reproduction of molds and mold components
US20030098530A1 (en) * 2001-10-10 2003-05-29 Kazuhiro Inoguchi Production method for ceramic structure and production method for ceramic honeycom structure
US20030220421A1 (en) * 2002-03-01 2003-11-27 Minebea, Co., Ltd. Low noise synthetic resin composition and method
US20040031642A1 (en) * 2002-06-05 2004-02-19 Kazuo Hokkirigawa Air purifying sound insulating wall and its applications
WO2004048463A1 (fr) * 2002-11-22 2004-06-10 Fabrizio Parodi Compositions polymeres pouvant etre rapidement chauffees par rayonnement electromagnetique, leurs utilisations et procedes de traitement associes
US20040258334A1 (en) * 2003-02-28 2004-12-23 Minebea Co., Ltd. Underwater sleeve bearing and application thereof
US6887288B2 (en) 2002-06-05 2005-05-03 Minebea Co., Ltd. Superfinishing grindstone
US7008196B2 (en) 2003-03-11 2006-03-07 Minebea Co. Ltd. Electrically motorized pump having a submersible sleeve bearing
EP1968761A1 (fr) * 2005-12-30 2008-09-17 Höganäs Ab Composition de poudre metallurgique
WO2009029993A1 (fr) * 2007-09-07 2009-03-12 The University Of Queensland Procédé de moulage par injection de métal
US20090202821A1 (en) * 2004-10-15 2009-08-13 Taisei Kogyo Co., Ltd. Method of making a porous sintered body, a compound for making the porous sintered body, and the porous sintered body
US20090224442A1 (en) * 2008-03-05 2009-09-10 Seiko Epson Corporation Method of manufacturing translucent ceramic and orthodontic member
CN103038006A (zh) * 2010-04-01 2013-04-10 维也纳科技大学 用于制造铝合金成型制品的方法
US20140145808A1 (en) * 2012-03-12 2014-05-29 Nitto Denko Corporation Rare-earth permanent magnet and method for manufacturing rare-earth permanent magnet
US20150159007A1 (en) * 2013-12-10 2015-06-11 Seiko Epson Corporation Mold material, molding method, mold object, and molding apparatus
US9556072B2 (en) 2009-06-25 2017-01-31 Basf Se Process for the continuous thermal removal of binder from a metallic and/or ceramic shaped body produced by injection molding, extrusion or pressing using a thermoplastic molding composition
US10155667B2 (en) * 2016-01-26 2018-12-18 Corning Incorporated System, process and related sintered article
EP3381591A4 (fr) * 2016-04-05 2019-04-24 Mitsubishi Heavy Industries Aero Engines, Ltd. Corps fritté, procédé de production de corps fritté, panneau de chambre de combustion et procédé de production de panneau de chambre de combustion
CN112658282A (zh) * 2020-12-03 2021-04-16 苏州复浩三维科技有限公司 一种金属3d打印脱脂溶液及其制备方法
CN114507065A (zh) * 2022-02-24 2022-05-17 新化县正能精细陶瓷有限公司 一种注塑成型氧化铝陶瓷材料及其注塑成型方法
US20230082902A1 (en) * 2019-12-11 2023-03-16 Basf Se Sinter powder (sp) containing a semi-crystalline terephthalate polyester
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JP3924671B2 (ja) * 1999-04-19 2007-06-06 第一工業製薬株式会社 金属粉末射出成形用組成物
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US5942566A (en) * 1997-07-03 1999-08-24 Advanced Ceramics Research, Inc. Ceramic feedstock composition for the manufacture of prototype elements
US20010050155A1 (en) * 2000-06-07 2001-12-13 Billiet Romain L. Method for rapid reproduction of molds and mold components
US6782940B2 (en) * 2000-06-07 2004-08-31 Romain L. Billiet Method for rapid reproduction of molds and mold components
US20030098530A1 (en) * 2001-10-10 2003-05-29 Kazuhiro Inoguchi Production method for ceramic structure and production method for ceramic honeycom structure
US8747729B2 (en) 2001-10-10 2014-06-10 Denso Corporation Product method for ceramic structure and production method for ceramic honeycomb structure
US20100102491A1 (en) * 2001-10-10 2010-04-29 Denso Corporation Product method for ceramic structure and production method for ceramic honeycomb structure
US20030220421A1 (en) * 2002-03-01 2003-11-27 Minebea, Co., Ltd. Low noise synthetic resin composition and method
US20030229161A1 (en) * 2002-03-01 2003-12-11 Minebea, Co., Ltd. Low-friction, high-dispersion synthetic resin compositon containing fine particles of RB ceramic or CRB ceramic and a method for its preparation
US7144932B2 (en) * 2002-03-01 2006-12-05 Minebea Co., Ltd. Low-friction, high-dispersion synthetic resin composition containing fine particles of RB ceramic or CRB ceramic and a method for its preparation
US7140778B2 (en) 2002-03-01 2006-11-28 Minebea Co., Ltd. Synthetic resin composites and bearings formed therefrom and method
US6887288B2 (en) 2002-06-05 2005-05-03 Minebea Co., Ltd. Superfinishing grindstone
US20040031642A1 (en) * 2002-06-05 2004-02-19 Kazuo Hokkirigawa Air purifying sound insulating wall and its applications
WO2004048463A1 (fr) * 2002-11-22 2004-06-10 Fabrizio Parodi Compositions polymeres pouvant etre rapidement chauffees par rayonnement electromagnetique, leurs utilisations et procedes de traitement associes
US20040258334A1 (en) * 2003-02-28 2004-12-23 Minebea Co., Ltd. Underwater sleeve bearing and application thereof
US7008196B2 (en) 2003-03-11 2006-03-07 Minebea Co. Ltd. Electrically motorized pump having a submersible sleeve bearing
US20090202821A1 (en) * 2004-10-15 2009-08-13 Taisei Kogyo Co., Ltd. Method of making a porous sintered body, a compound for making the porous sintered body, and the porous sintered body
US20160090327A1 (en) * 2004-10-15 2016-03-31 Taisei Kogyo Co., Ltd. Method of making a porous sintered body, a compound for making the porous sintered body, and the porous sintered body
US20190367419A1 (en) * 2004-10-15 2019-12-05 Taisei Kogyo Co., Ltd. Method of making a porous sintered body, a compound for making the porous sintered body, and the porous sintered body
US9272333B2 (en) * 2004-10-15 2016-03-01 Taisei Kogyo Co., Ltd. Method of making a porous sintered body, a compound for making the porous sintered body, and the porous sintered body
US11819917B2 (en) * 2004-10-15 2023-11-21 Taisei Kogyo Co., Ltd. Method of making a porous sintered body, a compound for making the porous sintered body, and the porous sintered body
EP1968761A4 (fr) * 2005-12-30 2010-06-16 Hoeganaes Ab Composition de poudre metallurgique
EP1968761A1 (fr) * 2005-12-30 2008-09-17 Höganäs Ab Composition de poudre metallurgique
WO2009029993A1 (fr) * 2007-09-07 2009-03-12 The University Of Queensland Procédé de moulage par injection de métal
US8420006B2 (en) * 2008-03-05 2013-04-16 Seiko Epson Corporation Method of manufacturing translucent ceramic and orthodontic member
US20090224442A1 (en) * 2008-03-05 2009-09-10 Seiko Epson Corporation Method of manufacturing translucent ceramic and orthodontic member
US9556072B2 (en) 2009-06-25 2017-01-31 Basf Se Process for the continuous thermal removal of binder from a metallic and/or ceramic shaped body produced by injection molding, extrusion or pressing using a thermoplastic molding composition
US20130101456A1 (en) * 2010-04-01 2013-04-25 Technische Universitat Wien Method for Producing Shaped Bodies from Aluminium Alloys
CN103038006A (zh) * 2010-04-01 2013-04-10 维也纳科技大学 用于制造铝合金成型制品的方法
US20140145808A1 (en) * 2012-03-12 2014-05-29 Nitto Denko Corporation Rare-earth permanent magnet and method for manufacturing rare-earth permanent magnet
US10770207B2 (en) * 2012-03-12 2020-09-08 Nitto Denko Corporation Rare-earth permanent magnet and method for manufacturing rare-earth permanent magnet
US20150159007A1 (en) * 2013-12-10 2015-06-11 Seiko Epson Corporation Mold material, molding method, mold object, and molding apparatus
US9849632B2 (en) * 2013-12-10 2017-12-26 Seiko Epson Corporation Mold material, molding method, mold object, and molding apparatus
US11111155B1 (en) 2016-01-26 2021-09-07 Corning Incorporated System, process and related sintered article
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US11746022B2 (en) 2016-01-26 2023-09-05 Corning Incorporated System, process and related sintered article
EP3381591A4 (fr) * 2016-04-05 2019-04-24 Mitsubishi Heavy Industries Aero Engines, Ltd. Corps fritté, procédé de production de corps fritté, panneau de chambre de combustion et procédé de production de panneau de chambre de combustion
US11511339B2 (en) 2016-04-05 2022-11-29 Mitsubishi Heavy Industries Aero Engines, Ltd. Sintered body, method of manufacturing sintered body, combustor panel, and method of manufacturing combustor panel
US11666967B2 (en) 2016-04-05 2023-06-06 Mitsubishi Heavy Industries Aero Engines, Ltd. Sintered body, method of manufacturing sintered body, combustor panel, and method of manufacturing combustor panel
US11643710B2 (en) 2018-02-21 2023-05-09 Jfe Steel Corporation Mixed powder for powder metallurgy
US20230082902A1 (en) * 2019-12-11 2023-03-16 Basf Se Sinter powder (sp) containing a semi-crystalline terephthalate polyester
CN112658282A (zh) * 2020-12-03 2021-04-16 苏州复浩三维科技有限公司 一种金属3d打印脱脂溶液及其制备方法
CN114507065A (zh) * 2022-02-24 2022-05-17 新化县正能精细陶瓷有限公司 一种注塑成型氧化铝陶瓷材料及其注塑成型方法

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EP0329475B1 (fr) 1994-01-26
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DE68912613T2 (de) 1994-05-11
EP0329475A2 (fr) 1989-08-23

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